IE42740B1 - Process for producing aluminium chlorohydroxides - Google Patents
Process for producing aluminium chlorohydroxidesInfo
- Publication number
- IE42740B1 IE42740B1 IE573/75A IE57375A IE42740B1 IE 42740 B1 IE42740 B1 IE 42740B1 IE 573/75 A IE573/75 A IE 573/75A IE 57375 A IE57375 A IE 57375A IE 42740 B1 IE42740 B1 IE 42740B1
- Authority
- IE
- Ireland
- Prior art keywords
- aluminium
- reaction
- process according
- hydrochloric acid
- amount
- Prior art date
Links
- -1 aluminium chlorohydroxides Chemical class 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001399 aluminium compounds Chemical class 0.000 claims abstract description 18
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910001570 bauxite Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
- C01F7/57—Basic aluminium chlorides, e.g. polyaluminium chlorides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
- Silicon Compounds (AREA)
Abstract
1488444 Aluminium chlorohydroxide SNAMPROGETTI SpA 21 March 1975 [28 March 1974] 12043/75 Addition to 1410087 Heading ClA An aluminium chlorohydroxide of formula Al 2 (OH) x Cl y (in which x is 1-4 and y is 5-2) is prepared by reacting hydrochloric acid with an aluminium oxide or hydroxide at a temperature exceeding 160‹ C. but not exceeding 270‹ C., the amount of aluminium compound available for reaction with the hydrochloric acid being at least the stoichiometric amount needed to produce AlCl 3 . Preferably Bayer alumina is used.
Description
This invention relates to a process for the production of aluminium chlorohydroxides.
The specification of our Patent No. 37607, to which the present application is an application for a patent of- addition, describes and claims a process for producing an aluminium chlorohydroxide having the formula Al„(0II) Cl wherein x is in the range from 1 to 3.5 and y x y is in the range* from 5 to 2.5, which process comprises reacting hydrochloric acid with an aluminium compound selected from aluminium oxides and hydroxides, which optionally contains water of crystallization, wherein, relative to the hydrochloric acid, the aluminium compound is employed in an amount in' excess of that required stoichiometrically to produce aluminium trichloride, the amount of aluminium compound not exceeding 4 times that required stoichiometrically to produce aluminium trichloride.
In that process the amount of aluminium compound used is preferably at least twice, more preferably at least 2.5 times, the stoichiometric amount necessary for obtaining aluminium trichloride, and the reaction preferably takes place I at temperatures in the range from 100 to 160 °C. The aluminium starting compound can be, for example, Bayer alumina.
According to the present invention, there is provided a process for producing an aluminium chlorohydroxide having the formula A1„(OH)Cl in which x is in the range from 1 to 4 and x y y is in the range from 5 to 2, which process comprises reacting -2hydrochloric acid with an aluminium compound selected from aluminium oxides and hydroxides, and which optionally contains water of crystallization, the reaction being effected at a temperature exceeding 160°C but not exceeding 270°C, the aluminium compound available for reaction with the hydrochloric acid being employed in an amount, relative to the hydrochloric acid, corresponding to or in excess of the stoichiometric amount of aluminium compound required to produce aluminium trichloride.
The starting aluminium compound can he, for example, Bayer alumina; the use of Bayer alumina (α-AlgOg.31^0) allows the reaction to be carried out in a relatively short reaction time, and a good yield of basic aluminium chlorohydroxides to be obtained.
Preferably the hydrochloric acid is an aqueous solution of hydrochloric acid having a HC1 content of from 30 to 37% by weight.
The excess of the aluminium compound employed can be, for example, an excess of the aluminium compound of up to 50% over that required stoichiometrically to produce aluminium trichloride.
The reaction is carried out at a temperature exceeding 160°C and not exceeding 27O°C, preferably at a pressure in the range from 0.1 to 50 kg/cm .
At the end of the reaction, there remains a solid constituted fundamentally by unreacted alumina, which can be separated and fed again to a subsequent reaction.
The advantage of using Bayer alumina with respect to other aluminium compounds can bo seen from tho following: the use of, for example, bauxite in the reaction causes Lhe formation of a solid containing silica and alumina at a ratio depending on tho particular reaction conditions used and on the bauxite type. Tho different crystallographic structures and the different granulometry cause, as regards bauxite and the other aluminium compounds, a lower reaction rate which means, with tho reaction at the same temperature, longer reaction times, sometimes of the magnitude of 2 to 5 times as long as those required when using Bayer alumina.
The other working conditions and tho possible uses of the obtained chlorohydroxides are as described in our earlier application, to which reference is made for all further details.
The present invention will now be described by the following Examples.
EXAMPLE 1 Use was made of Bayer alumina with parLiclos having Ί0 te 70 μ diameter, The roaction was carried ml as follows: 00 kg of dry Bayer alumina (α-Α190.? . 311,,0) were reacted with 110 kg of an aqueous solution of hydrochloric acid, containing 33% by weight of hydrogen chloride. The reaction was carried out in an enamelled steel reactor having a useful capacity of 100 litres, equipped with an anchor stirrer rotating at 80 revolutions per minute, and by introducing into tho reactor nitrogen up to a pressure of 0.5 kg/cm . The temperature was -442740 raised from the room temperature to 180 °C over 30 minutes, and the reaction was continued l'or 4 hours at 180 °C, the final pressure being 8 kg/cm . At the end there was a precipitate constituted by unreacted Dayer alumina, corresponding to 1% of the fed alumina. The final product did not need any nitration and had an ΛΙ^Ο^ content equal to 10.5% ami a density, determined at 20°C, equal Lo 1.40 g/cc. Chemical analysis confirmed that, if was a chlornhydrnxi de having tile formula Al^ (OH)^Clg. More particularly, a full chemical analysis of tiie product resulting from the separation of the precipitate was as follows: ai203 10.5% (by weight) Cl 21..0% I'e 45 ppm Na 0.12% Ti 10 ppm Si 10 pH 0.9 EXAMPLE 2 rise was made of the same starting material as used in Example 1, and the following reaction was carried out: 800 g of dry Bayer alumina were reacted with 1000 g of hydrochloric acid in tlie form of an aqueous solution containing 37¾ by weight of hydrogen chloride. The reaction was carried out in a reactor made of Hastelloy B and equipped with a magnetic dragging stirrer rotating at a rate of 200 revolutions per minute. (The word Hastelloy is a Trade Mark), -5427 40 Before .starting the reaction, the air in the reactor was replaced by nitrogen up to a residual pressure of 0.5 kg/cm . ·The. temperature was then raised Crom room temperature to 230°C over 30 minutes, and the reaction was continued for 6 hours at 230 °C, the final pressure being 25 kg/cm2.
At the end the temperature was lowered to 80°C, and 700 g of distilled water were added. Chemical analysis showed a precipitate constituted by unreaeted Bayer alumina corresponding to 2% of the fed alumina. The final product did not need any filtration and had an Al^O^ content equal to 19.5% by weight, and a density at 20 °C equal to 1.41 g/cc. The chemical analysis confirmed an aluminium chlorohydroxide having the formula Al2(0iI)4Cl2· More particularly, the total chemical analysis of the product resulting from the separation of the precipitate was as follows: ai2o3 19.5% Cl 14.4% Fe 45 ppm Na 0.12% Ti 10 ppm Si 10 ppm pH 1.7 EXAMPLE 3 The starting material was bauxite, ground in particle having sizes of from 120 to 180 Mosh, having tin; Following composition (by weight) -642740 ΛΙ Og 65% Fe203 4% Si.O2 12% T102 2% Tho reaction was carried out by reacting 145 kg of bauxite with 100 kg of hydrochloric ;vcid containing in aqueous solution 37% by weight of hydrogen chloride. The operating conditions and reactor were the same as those described in Example 1.
After the introduction of N^fat 0.5 kg/cm^) into tlie reactor, the temperature was raised to 180°C over 30 minutes, and the reaction was continued for 45 hours at 100 °C.
Af the end of the reaction, it was noted that only 25% of the fed bauxite had been dissolved, and the residual was unroactod precipitate.
Chemical analysis of the suspension, after Lhe separation of tho precipitate, showed the following composition:AlgO 13.5% Cl 20.7% Ee 1.5% Chemical analysis of the precipitate gave tlie following composition: Al203 54% S i.Og 10% Fe 0.9% Ch lorohydroxide obtained by l.he reaction has the formula A 1.,(011), ..01, r.
Claims (8)
1. A process for producing an aluminium chlorohydroxide having the formula A1„(OH) Cl in which x is in the range fr « x y 1 to 4 and y is in the range from 5 to 2, which process 5 comprises reacting hydrochloric acid with an aluminium compo selected from aluminium oxides and hydroxides,and which optionally contains water of crystallization, the reaction being effected at a temperature exceeding 160°C but not exceeding 270°C, the aluminium compound available for reacti' 10 with the hydrochloric acid being employed in an amount, relative to the hydrochloric acid, corresponding to or in excess of the stoichiometric amount of aluminium compound required to produce aluminium trichloride.
2. A process according to claim 1, wherein the aluminium 15 compound available for reaction is employed in an amount up · 1.5 times that required stoichiometrically to produce alumin: trichloride.
3. A process according to claim 1, wherein the aluminium compound available for reaction is employed in an amount up 20 to twice that required stoichiometrically to produce aluminii trichloride.
4. A process according to claim 1, wherein the aluminium compound available for reaction is employed in an amount up i four times that required stoichiometrically to produce 25 aluminium trichloride.
5. A process according to any preceding claim, wherein tl reaction is carried out by using a hydrochloric acid solutioi 8 <1 2 7 4 0 having a concentration of from 30 to 37% by weight.
6. A process according to any preceding claim, wherein the aluminium compound is Bayer alumina.
7. A process according to claim 1, substantially as described in any one of the foregoing Examples.
8. An aluminium chlorohydroxide whenever produced by a process according to any preceding claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT49835/74A IT1048280B (en) | 1974-03-28 | 1974-03-28 | PROCESS FOR THE PRODUCTION OF ALUMINUM HEART HYDROXIDES |
| KR7500811A KR800000972B1 (en) | 1974-03-28 | 1975-04-17 | Method for producing aluminum chlorohydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE42740L IE42740L (en) | 1975-09-28 |
| IE42740B1 true IE42740B1 (en) | 1980-10-08 |
Family
ID=26329390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE573/75A IE42740B1 (en) | 1974-03-28 | 1975-03-18 | Process for producing aluminium chlorohydroxides |
Country Status (26)
| Country | Link |
|---|---|
| US (1) | US4082685A (en) |
| JP (1) | JPS50137897A (en) |
| KR (1) | KR800000972B1 (en) |
| AR (1) | AR208191A1 (en) |
| AT (1) | AT339252B (en) |
| BE (1) | BE827261R (en) |
| CA (1) | CA1046238A (en) |
| CH (1) | CH605412A5 (en) |
| DD (1) | DD117207A5 (en) |
| DE (1) | DE2513786A1 (en) |
| DK (1) | DK123175A (en) |
| EG (1) | EG12901A (en) |
| FR (1) | FR2274561A2 (en) |
| GB (1) | GB1488444A (en) |
| IE (1) | IE42740B1 (en) |
| IT (1) | IT1048280B (en) |
| LU (1) | LU72127A1 (en) |
| MW (1) | MW1475A1 (en) |
| NL (1) | NL7503653A (en) |
| PH (1) | PH13282A (en) |
| RO (1) | RO65919A (en) |
| SE (1) | SE407399B (en) |
| TR (1) | TR18137A (en) |
| YU (1) | YU39209B (en) |
| ZA (1) | ZA751637B (en) |
| ZM (1) | ZM3675A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337596A (en) * | 1976-09-20 | 1978-04-06 | Osaka Soda Co Ltd | Production of basic aluminium polychloride |
| SE425847B (en) * | 1979-11-16 | 1982-11-15 | Boliden Ab | PROCEDURE FOR PREPARING WATER-SOLUBLE BASIC ALUMINUM CHLORIDE AND / OR BASIC ALUMINUM SULPHATE CHLORIDE |
| DE3147869A1 (en) * | 1981-12-03 | 1983-06-16 | Nefro-Pharma, Arzneimittelvertrieb GmbH, 8203 Oberaudorf | Aluminium chloride/hydroxide hydrate complex as a medicament for phosphate binding and process for its preparation |
| IT1229503B (en) * | 1989-01-25 | 1991-09-03 | Caffaro Spa Ind Chim | PROCEDURE FOR THE PREPARATION OF BASIC ALUMINUM COMPOUNDS. |
| SE8900478L (en) * | 1989-02-13 | 1990-08-14 | Boliden Kemi Ab | PROCEDURES FOR PREPARING POLYALUMINUM COMPOUNDS |
| DE4202937C2 (en) * | 1992-02-01 | 1995-10-26 | Air Lippewerk Recycling Gmbh | Process for the preparation of basic aluminum chloride solutions |
| CN1196711A (en) * | 1995-09-18 | 1998-10-21 | 德尔塔化学有限公司 | Polyaluminum chlorides and ployaluminum chlorosulfates methods and compositions |
| RU2129988C1 (en) * | 1997-01-20 | 1999-05-10 | АООТ "Капролактам" | Method of preparing basic aluminum chloride |
| US5938970A (en) | 1997-06-11 | 1999-08-17 | General Chemical Corporation | Polynucleate metal hydroxide compounds and method for their preparation |
| WO2003009811A2 (en) * | 2001-07-25 | 2003-02-06 | Haase Richard A | Processes and apparatus for the manufacture of polynuclear aluminum compounds and disinfectants, and polynuclear aluminum compounds and disinfectants from such processes and apparatus |
| US8268269B2 (en) * | 2006-01-24 | 2012-09-18 | Clearvalue Technologies, Inc. | Manufacture of water chemistries |
| RU2442748C1 (en) * | 2010-07-26 | 2012-02-20 | Кенже Рамазанович Рамазанов | Means to produce aluminum polyoxychlorides |
| RU2589164C1 (en) * | 2015-03-12 | 2016-07-10 | Открытое акционерное общество "Аурат" | Method of producing aluminium oxychloride |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1430449A (en) * | 1922-03-06 | 1922-09-26 | Grasselli Chemical Co | Method of preparing aluminum-chloride crystals |
| US1701510A (en) * | 1923-06-15 | 1929-02-12 | Sieurin Sven Emil | Production of oxide of aluminum |
| FR641623A (en) * | 1926-09-29 | 1928-08-07 | Ig Farbenindustrie Ag | Process for extracting alumina from clay and other aluminous raw materials by means of acids |
| US2413709A (en) * | 1943-03-31 | 1947-01-07 | John D Hoffman | Method of recovering alumina and hydrochloric acid |
| US2392153A (en) * | 1943-12-31 | 1946-01-01 | William R Warner & Co Inc | Production of basic aluminum chloride |
| US2947604A (en) * | 1956-12-07 | 1960-08-02 | Anaconda Co | Production of alumina |
| IT949756B (en) * | 1972-03-01 | 1973-06-11 | Snam Progetti | PROCESS FOR THE PRODUCTION OF ALUMINUM CHLOROHYDROXIDES |
| JPS5318996B2 (en) * | 1973-02-26 | 1978-06-17 |
-
1974
- 1974-03-28 IT IT49835/74A patent/IT1048280B/en active
-
1975
- 1975-01-01 AR AR258078A patent/AR208191A1/en active
- 1975-03-17 ZA ZA00751637A patent/ZA751637B/en unknown
- 1975-03-18 IE IE573/75A patent/IE42740B1/en unknown
- 1975-03-20 YU YU00701/75A patent/YU39209B/en unknown
- 1975-03-20 MW MW14/75A patent/MW1475A1/en unknown
- 1975-03-21 GB GB12043/75A patent/GB1488444A/en not_active Expired
- 1975-03-24 DK DK123175A patent/DK123175A/da not_active Application Discontinuation
- 1975-03-25 LU LU72127A patent/LU72127A1/xx unknown
- 1975-03-25 FR FR7509333A patent/FR2274561A2/en active Granted
- 1975-03-25 TR TR18137A patent/TR18137A/en unknown
- 1975-03-26 PH PH16976A patent/PH13282A/en unknown
- 1975-03-26 CH CH390475A patent/CH605412A5/xx not_active IP Right Cessation
- 1975-03-26 DD DD185047A patent/DD117207A5/xx unknown
- 1975-03-26 CA CA223,374A patent/CA1046238A/en not_active Expired
- 1975-03-26 RO RO7581808A patent/RO65919A/en unknown
- 1975-03-26 ZM ZM36/75A patent/ZM3675A1/en unknown
- 1975-03-26 NL NL7503653A patent/NL7503653A/en unknown
- 1975-03-27 BE BE154835A patent/BE827261R/en not_active IP Right Cessation
- 1975-03-27 AT AT236275A patent/AT339252B/en not_active IP Right Cessation
- 1975-03-27 DE DE19752513786 patent/DE2513786A1/en active Pending
- 1975-03-27 SE SE7503641A patent/SE407399B/en not_active IP Right Cessation
- 1975-03-27 US US05/562,782 patent/US4082685A/en not_active Expired - Lifetime
- 1975-03-28 JP JP50037010A patent/JPS50137897A/ja active Pending
- 1975-03-29 EG EG174/75A patent/EG12901A/en active
- 1975-04-17 KR KR7500811A patent/KR800000972B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2274561B2 (en) | 1977-04-15 |
| PH13282A (en) | 1980-02-29 |
| ZA751637B (en) | 1976-02-25 |
| LU72127A1 (en) | 1975-08-20 |
| FR2274561A2 (en) | 1976-01-09 |
| JPS50137897A (en) | 1975-11-01 |
| KR800000972B1 (en) | 1980-09-17 |
| ZM3675A1 (en) | 1975-12-22 |
| SE407399B (en) | 1979-03-26 |
| AU7932175A (en) | 1976-09-23 |
| AR208191A1 (en) | 1976-12-09 |
| IT1048280B (en) | 1980-11-20 |
| CH605412A5 (en) | 1978-09-29 |
| GB1488444A (en) | 1977-10-12 |
| DD117207A5 (en) | 1976-01-05 |
| ATA236275A (en) | 1977-02-15 |
| NL7503653A (en) | 1975-09-30 |
| DK123175A (en) | 1975-09-29 |
| EG12901A (en) | 1980-12-31 |
| BE827261R (en) | 1975-07-16 |
| SE7503641L (en) | 1975-09-29 |
| YU39209B (en) | 1984-08-31 |
| CA1046238A (en) | 1979-01-16 |
| YU70175A (en) | 1982-05-31 |
| RO65919A (en) | 1979-07-15 |
| TR18137A (en) | 1976-10-08 |
| AT339252B (en) | 1977-10-10 |
| US4082685A (en) | 1978-04-04 |
| MW1475A1 (en) | 1976-06-09 |
| IE42740L (en) | 1975-09-28 |
| DE2513786A1 (en) | 1975-10-02 |
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